Flame retardant halogenated polymer compositions

ABSTRACT

A halogenated aryl ether oligomer is formed by halogenation of an aryl ether oligomer and is useful as a flame retardant for flammable macromolecular materials. Typically, the halogenated aryl ether oligomer comprises the following repeating monomeric units: 
     
       
         
         
             
             
         
       
     
     wherein R is hydrogen or alkyl, especially C 1  to C 4  alkyl, Hal is halogen, m is at least 1, n is 0 to 3 and x is at least 2.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of the filing date of U.S.Provisional Application No. 60/926,374 filed Apr. 25, 2007, the entirecontents of which are incorporated herein by reference.

FIELD

This invention relates to flame retardant halogenated polymercompositions.

BACKGROUND

Decabromodiphenyl oxide (deca) and decabromodiphenylethane (deca-DPE)are commercially available materials widely used to flame retard variouspolymer resin systems. The structure of these materials is as follows:

One of the advantages of using deca and deca-DPE in polymer resins thatare difficult to flame retard, such as high-impact polystyrene (HIPS)and polyolefins, is that the materials have a very high (82-83%) brominecontent. This allows a lower load level in the overall formulation,which in turn serves to minimize any negative effects of the flameretardant on the mechanical properties of the polymer.

Despite the commercial success of deca, there remains significantinterest in developing alternative halogenated flame retardant materialsthat are equally or more efficient, not only because of economicpressures but also because they may allow lower flame retardantloadings, which in turn may impart improved performance properties.Improved properties, such as non-blooming formulations, or bettermechanical properties can potentially be met by producing polymeric oroligomeric flame retardant compounds. These types of materials wouldbecome entangled in the base resin polymer matrix, depending on thecompatibility, and hence should show fewer tendencies to bloom.

There are a number of commercially available flame retardant materialsthat can be considered oligomers or polymers of halogenated monomers.Examples of these monomers include tetrabromobisphenol A (TBBPA) anddibromostyrene (DBS), which have the following structures:

Commercially, TBBPA and DBS are typically not used in their monomericform, but are converted into an oligomeric or polymeric species. Oneclass of oligomers is the brominated carbonate oligomers based on TBBPA.These are commercially available from Chemtura Corporation (examplesinclude Great Lakes BC-52, Great Lakes BC-52HP™, and Great Lakes BC-58™)and by Teijin Chemical (FireGuard 7500 and FireGuard 8500). Theseproducts are used primarily as flame retardants for polycarbonate andpolyesters.

Brominated epoxy oligomers, based on condensation of TBBPA andepichlorohydrin, are commercially available and sold by Dainippon Inkand Chemicals under the Epiclon® series, and also by ICL IndustrialProducts (examples are F-2016 and F-2100) and other suppliers. Thebrominated epoxy oligomers find use as flame retardants for variousthermoplastics both alone and in blends with other flame retardants.

Another class of brominated polymeric flame retardants based on TBBPA isexemplified by Teijin FG-3000, a copolymer of TBBPA and1,2-dibromoethane. This aralkyl ether finds use in ABS and otherstyrenic polymers. Alternative end-groups, such as aryl or methoxy, onthis polymer are also known as exemplified by materials described inU.S. Pat. No. 4,258,175 and U.S. Pat. No. 5,530,044. The non-reactiveend-groups are claimed to improve the thermal stability of the flameretardant.

TBBPA is also converted into many other different types of epoxy resincopolymer oligomers by chain-extension reactions with other difunctionalepoxy resin compounds, for example, by reaction with the diglycidyletherof bisphenol A. Typical examples of these types of epoxy resin productsare D.E.R.™ 539 by the Dow Chemical Company, or Epon™ 828 by HexionCorporation. These products are used mainly in the manufacture ofprinted circuit boards.

DBS is made for captive use by Chemtura Corporation and is sold asseveral different polymeric species (Great Lakes PDBS_(—)80™, GreatLakes PBS-64HW™, and Firemaster CP44-HF™) to make poly(bromostyrene)type flame retardants. These materials represent homopolymers orcopolymers. Additionally, similar brominated polystyrene type flameretardants are commercially available from Albemarle ChemicalCorporation (Saytex® HP-3010, Saytex® HP-7010, and PyroChek 68PB). Allthese polymeric products are used to flame retard thermoplastics such aspolyamides and polyesters.

Unfortunately, one of the key drawbacks of the existing brominatedpolymer materials is their relatively low bromine content, which makesthem less efficient as a flame retardant and consequently typically hasa negative effect on the desirable physical properties of the flameretardant formulations containing them, such as impact strength. Forexample, whereas deca and deca-DPE contain 82-83% bromine, oligomers orpolymers based on the brominated monomers mentioned above generally havea bromine content in the range of 52%-68%, depending on the material.This therefore typically requires a flame retardant loading level in apolymer formulation significantly higher than that required for deca,often resulting in inferior mechanical properties for the formulation.

Other considerations also influence the impact the flame retardant hason the final properties of the formulated resin. These considerationsinclude the flame retardant thermal stability and the compatibility withthe host resin. In situations where these other considerations arerelatively constant, the bromine content, and hence flame retardant loadlevel, has a major influence on the properties of the overallformulation.

To address the need for flame retardant materials that to not detractfrom the mechanical properties of the target resin, we have nowdeveloped a family of materials that can be classified as halogenated,and particularly brominated, aryl ether oligomers. In particular, wehave found that the use of these halogenated aryl ether oligomersresults in superior mechanical properties in resins such as HIPS andpolyolefins and that the materials also provide excellent properties inengineering thermoplastics such as polyamides and polyesters. The arylether oligomers can be halogenated to a higher level than the oligomersand polymers that are commercially available today, which should have apositive effect on their mechanical property performance. It is alsofound that these aryl aryl ether oligomers, even at lower levels ofhalogenation, give formulations with acceptable mechanical propertiesJapanese Unexamined Patent Application Publication 2-129,137 disclosesflame retardant polymer compositions in which the polymer is compoundeda with halogenated bis(4-phenoxyphenyl)ether shown by general formula[I]:

in which X is a halogen atom, a and d are numbers in the range of 1-5,and b and c are numbers in the range of 1-4. However, the flameretardant is produced by brominating the bis(4-phenoxyphenyl)ether as adiscrete compound and not an oligomeric material obtained bypolymerizing an aryl ether monomer. In contrast, employing a materialhaving an oligomeric distribution as in the present invention isbelieved to improve its performance properties as a flame retardant.

In an article entitled “Synthesis and Stationary Phase Properties ofBromo Phenyl Ethers, Journal of Chromatography, 267 (1983), pages293-301, Dhanesar et al disclose a process for the site-specificbromination of phenyl ethers containing from 2 to 7 benzene rings. Againthe ethers appear to be discrete compounds with no oligomericdistribution and, although the products are said to be useful in theseparation of organic compounds, no reference is given to their possibleuse as flame-retardants.

SUMMARY

In one aspect, the present invention resides in a halogenated aryl etheroligomer formed by halogenation of an aryl ether oligomer.

Conveniently, the halogen content of the halogenated aryl ether oligomeris in the range of about 50 to about 83 wt %, such as in the range ofabout 65 to about 80 wt % of the oligomer. Generally, the halogencomprises bromine.

Conveniently, the halogenated aryl ether oligomer has an average ofleast 3 aryl and typically at least 5 aryl rings. Generally, themolecular weight of the halogenated oligomer is up to 1,000,000 Daltons.

In one embodiment, the halogenated aryl ether oligomer comprises thefollowing repeating monomeric units:

wherein R is hydrogen or alkyl, especially C₁ to C₄ alkyl, Hal ishalogen, normally bromine, m is at least 1, n is 0 to 3 and x is atleast 2, such as 3 to 100,000, for example 5 to 20.

In a further aspect, the present invention resides in a flame retardantpolymer composition comprising (a) a flammable macromolecular materialand (b) a halogenated aryl ether oligomer flame retardant formed byhalogenation of an aryl ether oligomer.

In yet a further aspect, the present invention resides in a flameretardant polymer composition comprising (a) a flammable macromolecularmaterial and (b) a halogenated aryl ether oligomer flame retardantformed by halogenation of an aryl ether oligomer wherein saidhalogenated aryl ether oligomer comprises the following repeatingmonomeric units:

wherein R is hydrogen or alkyl, especially C₁ to C₄ alkyl, Hal ishalogen, normally bromine, m is at least 1, n is 0 to 3 and x is atleast 2, such as 3 to 100,000, for example 5 to 20.

Conveniently, said halogenated aryl ether oligomer also comprises endgroups each independently comprising an alkyl, alkoxy, aryl, aryloxy,hydrogen, halogen or hydroxyl group.

In still yet a further aspect, the present invention resides in a flameretardant polymer composition comprising (a) a flammable macromolecularmaterial and (b) a halogenated aryl ether flame retardant having thefollowing formula:

wherein each R¹ is independently selected from hydrogen, hydroxy,halogen and alkyl, wherein each R² is independently selected fromhydrogen, hydroxy, halogen and alkyl, provided at least one R² andnormally at least one R¹ is halogen, normally bromine, n is 5, m is 4,and x is from 1 to 10, for example from 2 to 6.

Conveniently, the flammable macromolecular material (a) is athermoplastic polymer, such as polystyrene, poly(acrylonitrile butadienestyrene), a polycarbonate, a polyolefin, a polyester and/or a polyamide.

In one embodiment, the flammable macromolecular material (a) ispolystyrene and the amount of halogenated aryl ether oligomer flameretardant in the composition is between about 5 and 25 wt %, such asbetween about 10 and 20 wt %.

In another embodiment, the flammable macromolecular material (a) ispolypropylene and the amount of halogenated aryl ether oligomer flameretardant in the composition is between about 20 and 50 wt %, such asbetween about 25 and 40 wt %.

In a further embodiment, the flammable macromolecular material (a) ispolyethylene and the amount of halogenated aryl ether oligomer flameretardant in the composition is between about 5 and 35 wt %, such asbetween about 20 and 30 wt %.

In a further embodiment, the flammable macromolecular material (a) is apolyamide or a polyester and the amount of halogenated aryl etheroligomer flame retardant in the composition is between about 5 and 25 wt%, such as between about 10 and 20 wt %.

Alternatively, the flammable macromolecular material (a) is athermosetting polymer, such as an epoxy resin, an unsaturated polyester,a polyurethane and/or a rubber.

DESCRIPTION OF THE EMBODIMENTS

Described herein is a halogenated aryl ether oligomer formed byhalogenation, particularly bromination, of an aryl ether oligomer anduse of the halogenated oligomer as a flame retardant for flammablemacromolecular polymers. Suitable macromolecular polymers includethermoplastic polymers, such as polystyrene, poly(acrylonitrilebutadiene styrene), polycarbonates, polyolefins, polyesters andpolyamides, and thermosetting polymers, such as epoxy resins,unsaturated polyesters, polyurethanes and rubbers.

The term “oligomer” is used herein to mean a compound formed byoligomerization of one or more monomers so as to have repeating unitsderived from said monomer(s) irrespective of the number of saidrepeating units. Because the aryl ether precursor used to the producethe present flame retardant is produced by an oligomerization process,the precursor and the halogenated product will generally have adistribution of molecular weight. In particular, the oligomer generallyhas an average of least 3 aryl and typically at least 5 aryl rings, withthe average molecular weight of the halogenated oligomer being up to1,000,000 Daltons.

Typically, the present halogenated aryl ether oligomer comprises thefollowing repeating monomeric units:

wherein R is hydrogen or alkyl, especially C₁ to C₄ alkyl, Hal ishalogen, m is at least 1, n is 0 to 3 and x is at least 2, such as 3 to100,000, for example 5 to 20. The halogen can be fluorine, chlorine,bromine and/or iodine, especially bromine. Generally, the halogenatedaryl ether oligomer also comprises end groups each independentlycomprising an alkyl, alkoxy, aryl, aryloxy, hydrogen, halide or hydroxylgroup.

In one embodiment, the halogenated aryl ether oligomer flame retardanthas the following formula:

wherein each R¹ is independently selected from hydrogen, hydroxy,halogen and alkyl, wherein each R² is independently selected fromhydrogen, hydroxy, halogen and alkyl, provided at least one R² ishalogen, normally bromine, n is 5, m is 4, and x is from 1 to 100,000,for example from 3 to 20.

Generally, the halogen content of the present halogenated aryl etheroligomer is in the range of about 50 to about 83 wt %, such as in therange of about 65 to about 80 wt % of the oligomer.

In another embodiment, the flame retardant used herein comprises ahalogenated aryl ether having the following formula:

wherein each R¹ is independently selected from hydrogen, hydroxy,halogen and alkyl, wherein each R² is independently selected fromhydrogen, hydroxy, halogen and alkyl, provided at least one R² andnormally at least one R¹ is halogen, normally bromine, n is 5, m is 4,and x is from 1 to 10, for example from 2 to 6. In the case of thisembodiment, the halogenated aryl ether may have an oligomericdistribution or may be a discrete compound.

The present flame retardant is produced by halogenation, normallybromination, of a polyaryl ether precursor, which in turn can be made byoligomerization of a hydroxyhaloaryl material, such as bromophenol, orreaction of a dihalo aryl material, such as dibromobenzene, with adihydroxyaryl material, such as resorcinol, using an ether synthesis,such as the Ullmann ether synthesis. In this process, the reagents areheated under reflux, typically at about 125° C. to about 200° C., in apolar organic solvent, such as N,N-dimethylformamide or benzophenone, inthe presence of a strong base and a copper-containing catalyst.

A representative disclosure of the Ullmann ether synthesis is given byLaskoski et al. in “Oligomeric Cyanate Ester Resins: Application of aModified Ullmann Synthesis in the Preparation of ThermosettingPolymers”, Journal of Polymer Science. Part A. polymer Chemistry, Vol.44, (2006), pages 4559-4565.

Bromination of the resultant polyaryl ether is readily achieved by thereaction of the polyaryl ether with bromine in the presence of a Lewisacid catalyst, such as aluminum chloride. Depending on the amount ofbromine desired to be introduced into the aryl ether oligomer, theweight ratio of bromine to oligomer employed in the bromination reactionis typically between about 1:1 and about 100:1, such as between about3:1 and about 20:1. The final brominated aryl ether oligomer isgenerally arranged to have at least one, and typically between 2 and 4bromine atoms per aryl ether repeating unit of the oligomer.

Alternatively, bromine chloride may be used as the brominating agent togenerate the desired product in similar fashion. In this case, a smallamount of organically-bound chlorine would also be present, but wouldnot detract from the properties of the final flame retardant.

The resultant halogenated aryl ether oligomer can be used as a flameretardant for many different polymer resin systems because of its highthermal stability and also because of its relatively high halogencontent compared with existing polymeric flame retardant products, suchas brominated polystyrenes. Generally, the halogenated aryl etheroligomer is employed as a flame retardant with thermoplastic polymers,such as polystyrene, high-impact polystyrene (HIPS), poly(acrylonitrilebutadiene styrene) (ABS), polycarbonates (PC), PC-ABS blends,polyolefins, polyesters and/or polyamides. With such polymers, the levelof the halogenated oligomer in the polymer formulation required to givea V-0 classification when subjected to the flammability test protocolfrom Underwriters Laboratories is generally within the following ranges:

Polymer Useful Preferred Polystyrene 5 to 25 wt % 10 to 20 wt %Polypropylene 20 to 50 wt %  25 to 40 wt % Polyethylene 5 to 35 wt % 20to 30 wt % Polyamide 5 to 25 wt % 10 to 20 wt % Polyester 5 to 25 wt % 10 to 20 wt %.

The present halogenated aryl ether oligomer can also be used withthermosetting polymers, such as an epoxy resins, unsaturated polyesters,polyurethanes and/or rubbers. Where the base polymer is a thermosettingpolymer, a suitable flammability-reducing amount of the oligomer isbetween about 5 wt % and about 35 wt %, such as between about 10 wt %and about 25 wt %.

Typical applications for polymer formulations containing the presenthalogenated aryl ether oligomer as a flame retardant include automotivemolded components, adhesives and sealants, fabric back coatings,electrical wire and cable jacketing, and electrical and electronichousings, components and connectors. In the area of building andconstruction, typical uses for the present flame retardant include selfextinguishing polyfilms, wire jacketing for wire and cable, backcoatingin carpeting and fabric including wall treatments, wood and othernatural fiber-filled structural components, roofing materials includingroofing membranes, roofing composite materials, and adhesives used to inconstruction of composite materials. In general consumer products thepresent flame retardant can be used in formulation of appliance parts,housings and components for both attended and unattended applianceswhere flammability requirements demand.

The invention will now be more particularly described with reference tothe following non-limiting Examples.

Examples 1 to 7 Bromination of Aryl Ether Resin

Bromine (3176 g, 19.87 mol) was added to a solution of 500 g of arylether resin (Santovac OS-124) in 1 L of dichloroethane containing 6.5 gof AlCl₃ catalyst. The Santovac OS-124 is an aryl ether resin containingfive aryl rings connected in the meta position and was used to simulatean oligomeric material. After work-up, the brominated resin was isolatedto give 2013.6 g of a pale cream powder as the product. The materialanalyzed to contain 75.7% bromine and the TGA analysis showed a 5% wtloss at 420° C. Differential Scanning Calorimetry (DSC) analysis showeda glass transition (Tg) at 154° C.

Several additional materials were prepared in similar fashion to givebrominated aryl ether materials containing different levels of bromineor different ring connectivities, as shown in Table 1. The brominationlevel was found to influence the observed glass transition temperaturesand melt-ranges of the products.

TABLE 1 Oligomer % Tg, ° C. Visual Melt Example Type^((a)) Bromine (DSC)Range, ° C. 1 5-meta 75.7 154 177-211 2 5-meta 65.5 77.0  87-109 35-meta 74.7 150.8 160-183 4 5-meta 80.0 192.1 204-221 5 6-meta 74.8160.5 184-198 6 3-para 72.6 85.3 185-241 7 4-para 70.8 130.5 168-196^((a))Nomenclature: 5-meta means 5 aryl rings connected by all metalinkages.

Example 8 Polyarylether Synthesis from Resorcinol and 1,4-Dibromobenzene

A reaction flask was charged with resorcinol (15.0 g, 0.137 mole),1,4-dibromobenzene (32.3 g, 0.137 mole), N,N-dimethylformamide (205 g;2.58 mole), toluene (20 g, 0.22 mole), and a 50% solution of KOH, whichwas made by dissolving 90% KOH (17.05 g, 0.274 mole) in DI water. Theamount of base typically ranges from 1.8 to 2.2 mole per mole ofresorcinol. The reaction mixture was heated to reflux to azeotropicallyremove the water. After the theoretical amount of water was removed,most of the toluene was stripped from the reaction flask to a final pottemperature of 148-150° C. Then, the reaction was cooled to −120° C. andCuI (0.52 g, 0.00274 mole) and 1,10-phenanthroline (0.74 g, 0.0041 mole)were added simultaneously under a heavy nitrogen stream. The reactionflask was blanketed under nitrogen and the mass heated to reflux(˜150-155° C.) for 24 hour and then cooled for workup. The worked upinvolved acidification of the mixture to a pH of 2-3 with 2% HClfollowed by extraction with methylene chloride or chloroform. Theorganic phase was stripped to give a viscous resin product residue withan isolated yield=92%. GPC analysis of the product gave a molecularweight (Mw) of 605 and polydispersity (Pd) of 1.97.

GPC analysis of various reaction products produced by this approach gavean Mw ranging from 600 to 3100.

Example 9 Polyarylether Synthesis from 3-Bromophenol in DMF/Toluene

3-Bromophenol (100 g, 0.58 mole), toluene (700 g), and 50% KOH (72 g,0.58 mole) were added to a standard reaction flask. The contents wereheated to reflux and the water was removed azeotropically. An additional540 grams of toluene was stripped from the reaction flask. The contentsof the flask were cooled to 100° C. and DMF (467 grams), CuI (0.22 g,0.0012 mole), and 1,10-phenanthroline (0.31 g, 0.0017 mole) were added.The contents of the flask were heated back to reflux. Additional toluenewas stripped until the temperature reached 140° C. and bromobenzene(4.55 grams, 0.029 mole) was then added. After the reaction wascomplete, the product was worked up to give a viscous amber coloredresin in 93.1% yield. This product polymer had a molecular weight by GPCanalysis of 2270 Mw.

Example 10 Polyarylether Synthesis from 4-Bromophenol with Benzophenoneas Solvent

A reaction flask was charged with 4-bromophenol (232.5 g, 1.34 mole),benzophenone (1435 g, 8.04 mole), and toluene (900 g, 1.34 mole). Theflask was purged with N₂ and was heated to <100° C. to dissolve thebenzophenone. A 50% solution of KOH was prepared by dissolving 90% KOH(83.5 g, 1.34 mole) in 83.5 g DI water. The KOH solution was added tothe flask over a period of 5 minutes and contents of the flask wereheated to reflux. The water was removed azeotropically and the toluenewas distilled out. Bromobenzene (10.5 g, 0.07 mole) was added along witha solution of CuCl (1.33 g, 0.0134 mole) dissolved in pyridine (90 g,0.134 mole). The reaction was held at 204° C. for 5 hours. The reactionwas cooled and worked up to give 165.7 g (65% yield) of light tansolids. Analysis by GPC (THF solvent system) gave Mw=1790 and Pd=1.70(not all the material was soluble).

Due to lack of complete solubility in the solvent used for GPCdeterminations, a secondary analysis of molecular weight was conductedbased on DSC. A series of model compounds of para aryl ethers containing3, 4, and 5 rings were analyzed by DSC and found to have melting pointsthat fit to a straight line equation. Included in this analysis wasdiphenyl ether, which fit the line as expected. The mp data is asfollows for the para model series (2 ring through 5 ring): 26, 75.6,108.2, 147.4° C. This line was used to estimate the number of arylgroups on the polymer that was made, which would only be a crudeestimation of molecular weight. By this approach, the number of arylrings was predicted to be 8.

Examples 11 and 12 Bromination of Aryl Ethers from 4-BromophenolPolymerization

A reaction flask was charged with 100.0 g of the polyphenyl etherproduced in Example 10, 600 ml of chloroform and 10.2 g of aluminumchloride. The resulting slurry was heated to reflux (60° C.) and 1202.8g of dry bromine was added over 6 hours while maintaining reflux. Thereaction mass was held at reflux temperature for 2 hours and worked upto give a solid precipitate. The resulting polymeric product (223.2 g),was a tan solid, with the following analysis: 68.8% OBr, melt range230-313° C. The properties of the product are shown in Table 2.

The above bromination method was repeated to give a brominatedoligomeric aryl ether material containing a different level of bromine,as shown in Table 2.

Examples 13 and 14 Bromination of Aryl Ethers from 3-BrPhOHPolymerization

A large-scale reaction from Example 9 was conducted by using a 0.20 molratio of bromobenzene endcap to 3-bromophenol, generating a materialthat analyzed to have a slightly lower molecular weight by GPC of 700Mw. A reaction flask was charged with 108.2 g of this polyphenyl ether,1000 ml of chloroform and 10.8 g of aluminum chloride. The resultingslurry was heated to reflux (60° C.) and 1044.1 g of dry bromine wasadded over 8 hours while maintaining reflux. The reaction mass was heldat reflux temperature for 1 hour and worked up to give a solidprecipitate. The resulting polymeric product (319.9 g), was a brownsolid, with the following analysis: 70.2% OBr, melt range 141-161° C.,DSC showed a glass transition (Tg) at 117° C. The properties of theproduct are shown in Table 2.

The above bromination method was repeated to give a brominatedoligomeric aryl ether material containing a different level of bromine,as shown in Table 2.

By comparing the results in Table 2, it will be seen that by varying theregiochemistry of the oligomer (meta vs para), oligomers with differentglass transition temperatures and visual melt-ranges were produced. Itis also possible to prepare a mixed oligomer having a blend of meta andpara connectivities by using the appropriate reagents and ratios duringthe reaction.

TABLE 2 Oligomer GPC % Tg, ° C. Melt Example Type (MW)^((a)) Bromine(DSC) Range, ° C. 11 Para 1790 68.8 >240 230-313 12 Para 1700 58.7 >240216-293 13 Meta 700 70.2 117 141-161 14 Meta 1020 64.1 123 141-164^((a))GPC analysis was conducted on the oligomer prior to bromination.The para samples were only partially soluble.

Example 15 Compounding of Brominated Aryl Ether Oligomers in HIPS Resin

The brominated aryl ether oligomers prepared in Examples 1 to 4(Table 1) were separately compounded with HIPS (high impact polystyrene)resin formulations containing antimony oxide (ATO) synergist using atwin-screw extruder with barrel temperatures of 200-220° C. Forcomparison, similar formulations were prepared using deca and deca-DPEas the flame retardants. The resultant formulations wereinjection-molded into test bars and evaluated as shown in Table 3. Themechanical property and MFI tests were conducted according to the normalASTM methods. The glass-transition temperatures of the brominated arylether oligomers were all below the compounding temperatures of theresin, indicating that the oligomers would be melt-blendable in thissystem. Note that deca and deca-DPE are not melt-blendable and act asfiller type materials. This data shows correlation between melt flowindex (MFI) of the compounded material and the Tg of the FR that wasused, which is somewhat expected. The data also shows that the Vicatsoftening point is not really influenced by the flame retardant typethat was used, except for the lower Tg sample, which is also reasonable.

TABLE 3 Formulation No 15-A 15-B 15-C 15-D 15-E 15-F FR Deca Deca-DPEExample 1 Example 2 Example 3 Example 4 FR, % Br 83 “83”   75.7 65.574.7 80.0 FR Tg, ° C. NA NA 154 77 151 192 Formulation Polystyrene Resin77.3 77.3  75.95 73.6 75.7 76.8 FR 14.0 14.0  15.35 17.7 15.6 14.5 ATO3.5 3.5 3.5 3.5 3.5 3.5 Anox PP-18 0.2 0.2 0.2 0.2 0.2 0.2 Kraton D11015.0 5.0 5.0 5.0 5.0 5.0 Test Results MFI (g/10 min) 9.7 7.7 9.4 19.2 9.78.9 Vicat, ° C. 96.2 97.6  98.7 92.9 99.2 100.4 Izod Notched ImpactStrength 2.1  2.05 3.2 2.5 2.7 2.5 (ft-lb/in) UL-94 ( 1/16″) V-0 V-0 V-0V-0 V-0 V-0

The surprising result lies in the impact strength data. When comparingthe formulations with the two control samples, the aryl ether oligomersystems show an actual increase in impact strength. A wide range of Tgcan be used while still obtaining good mechanical properties. Thisresult could be due to an improvement in resin-FR compatibility, domainsize of the FR material in the test bars, or some other factor. Thesedata indicate that the properties of the final formulation can beoptimized by adjusting the FR oligomer glass transition temperature.This would not be possible with brominated small molecules, as theytypically are high-melting solids.

Example 16 Compounding of Brominated Aryl Ether Oligomers in HIPS Resin

The brominated aryl ether oligomers prepared in Example 12 (Table 2)were separately compounded with HIPS (high impact polystyrene) resinformulations containing antimony oxide synergist using a twin-screwextruder with barrel temperatures of 200-220° C. These formulations wereinjection-molded into test bars and evaluated as shown in Table 4. Twoof these FR oligomer materials have Tg values below the compoundingtemperatures and two have Tg values somewhere above that temperature.The latter two would, therefore, not be melt-blendable and the resultingMFI values are expectedly lower. Interestingly, these samples based onthe para aryl ether gave reduced impact strength properties and thosebased on the meta aryl ethers gave good impact strength values. Thiscould be a reflection of different compatibilities between the FR typesand the resin, or related to how the materials coalescence informulation upon cooling, or some other factor.

TABLE 4 Formulation No. 16-A 16-B 16-C 16-D 16-E FR Deca Example ExampleExample Example 12 11 13 14 FR, % Br 83 58.7 68.8 70.2 64.1 FR Tg, ° C.NA >240 >240 117 123 Formulation Polystyrene Resin 77.3 71.5 74.4 74.5573.2 FR 14.0 19.8 16.9 16.55 18.1 ATO 3.5 3.5 3.5 3.5 3.5 Anox PP-18 0.20.2 0.2 0.2 0.2 Kraton D1101 5.0 5.0 5.0 5.0 5.0 Test Results MFI (g/10min) 9.7 5.6 5.7 12.1 11.7 Vicat, ° C. 96.2 99.6 98.2 97.8 98.1 IzodNotched 2.1 1.2 0.7 2.2 1.9 Impact Strength (ft-lb/in) UL-94 ( 1/16″)V-0 V-1 V-1 V-0 V-0

Example 17 Compounding of Brominated Aryl Ether Oligomers in HIPS Resin

Since the impact strength for some of the formulations in Examples 15and 16 was actually higher than the standard deca type control runs, astudy was conducted in which the flame retardant of Example 1 wasemployed and impact modifier (Kraton D1101) was reduced, as shown inTable 5. This study shows that the impact modifier can indeed be reducedor potentially eliminated from a HIPS formulation and still be as goodas (or close to) the deca control formulation, and that there is roomfor further formulation optimization of properties.

TABLE 5 Formulation No 17-A 17-B 17-C 17-D FR Deca Example 1 Example 1Example 1 FR, % Br 83 73.1 73.1 73.1 FR Tg, ° C. NA 148 148 148Formulation Polystyrene Resin 77.3 75.9 78.4 80.9 FR 14.0 15.4 15.4 15.4ATO 3.5 3.5 3.5 3.5 Anox PP-18 0.2 0.2 0.2 0.2 Kraton D1101 5.0 5.0 2.50 Test Results MFI (g/10 min) 9.7 12.5 14.3 15.5 Vicat, ° C. 96.2 99.399.1 98.6 Izod Notched Impact 2.1 2.6 2.2 1.8 Strength (ft-lb/in) UL-94( 1/16″) V-0 V-0 V-0 V-0

Example 18 Compounding of Brominated Aryl Ether Oligomers in Polyamide

The brominated aryl ether oligomers shown in Table 1 were compoundedwith glass-reinforced PA66 resin containing antimony oxide synergists.These formulations were molded into test bars and evaluated as shown inTable 6. This set of data compares the oligomeric aryl ether flameretardants with a commercially available brominated polystyrene (Saytex™HP-3010). The results show that the aryl ether is more efficient,showing a V-0 at 13.3% loading and a strong V-0 at 16% loading, ascompared with the 20% loading for the HP-3010 material. The data alsoshows a slight improvement in mechanical properties with tensilestrength being about the same, but tensile elongation showing about a20% improvement.

TABLE 6 Formulation No. 18-A- 18-B 18-C 18-D 18-E FR None HP-3010 Ex. 1Ex. 1 Ex. 2^(a) FR, % Br — 68 75.7 75.7 63.0 Formulation PA66 Resin 7041.2 50.65 47.15 42.65 Glass Fiber 30 30 30 30 30 FR 20 13.5 16.0 19.8ATO 8.45 5.5 6.5 7.2 Magnesium stearate 0.35 0.35 0.35 0.35 Test ResultsTensile Strength, Kpsi 26.9 21.3 21.4 21.0 NA Tensile Elongation, % 3.911.89 2.39 2.22 NA Sprial flow, in. 23.8 30.4 26.3 28.2 NA Viscosity,Pa-s @ 168.8 103.2 106.0 100.8 NA 1000 s⁻¹ UL-94 total burn time NA 5 362 14 (5 bars), s UL-94 ( 1/32″) FAIL V-0 V-0 V-0 V-0 ^(a)A scale-up ofExample 2; Analysis: m.p. 96-113° C., % Bromine = 63.0%

In order to determine if the improved flame retardant efficiency is aresult of the higher bromine content, or is related to the structure ofthe oligomer, a lower bromine content sample was also tested. Theresults showed that at the same load level as the 68% bromine contentbrominated polystyrene material (i.e. lower overall bromine content),the formulation was a strong V-0. This indicated that the structure iscontributing to the improved FR efficiency.

Example 19 Compounding of Different Flame Retardants in Polypropylene

The brominated aryl ether oligomer of Example 3 was compounded withProfax 6323 polypropylene homopolymer containing an antimony oxidesynergist and, for comparison, similar formulations were prepared usingdeca and deca-DPE as the flame retardant. The formulations werecompounded using a twin-screw extruder with barrel temperature of about200° C., injection-molded into test bars and evaluated as shown in Table7.

TABLE 7 Formulation No 19-A 19-B 19-C 19-D Profax 6323 PP homopolymer(%) 100 59 55.8 59 Deca (%) 35 Bromo(polyaryl ether) Ex. 3 (%) 38.2Deca-BDE (%) 35 ATO (%) 6 6 6 UL-94 Rating V-0 V-0 V-0 MFI (g/10 min)12.4 11.2 47.4 12.1 HDT (° C.), 264 psi 84 112 120 117

These results show a significant increase in the melt flow property witha slightly higher increase in Heat Deflection Temperature (HDT) for theoligomeric FR product as compared with the deca and deca-DPE controlsamples.

The formulations were also subjected to a bloom test by placing the ULtest bars in an oven at 80° C. The bars were pulled out of the oven at24 hours and after 1 week and wiped with a black cloth to pick up bloomif present. Bloom is a migration of the flame retardant or otheradditive to the surface and usually shows as a visible dust on the testcloth. There was no bloom present on the oligomeric FR formulation bars,whereas the other two flame retardant formulations showed bloom.

Example 20 Compounding of Different Flame Retardants in Low DensityPolyethylene

The brominated aryl ether oligomer of Example 3 was compounded withPetrothene NA820000 NT low density polyethylene and, for comparison,similar formulations were prepared using deca and deca-DPE as the flameretardant. The formulations were compounded using a twin-screw extruderwith barrel temperature of about 190° C., injection-molded into testbars and evaluated as shown in Table 8.

TABLE 8 Formulation No 20-A 20-B 20-C 20-D Resin Petrothene NA820000 NTLDPE FR None Deca Ex. 3 Deca-BDE FR % 24 26.2 24 MFI (g/10 min) 1.331.54 2.38 1.35 HDT (° C.), 264 psi 39.6 42.1 66.9 42.3 FlexuralProperties Strength (ksi) 1.2 1.5 2.3 1.5 Modulus (ksi) 19.1 27.1 56.527 UL-94 Rating FAIL V-0 V-0 V-0

For this resin system, the MFI and HDT properties both increased whenthe oligomeric flame retardant was used as compared the brominatedcontrol samples. Additionally, it was found that the flexural propertiesalso increased. A bloom test was conducted as described in the previousexample and the oligomeric FR formulation showed just a faint trace ofbloom, whereas the deca formulation showed a large amount of bloom onthe test cloth.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For this reason, then, reference shouldbe made solely to the appended claims for purposes of determining thetrue scope of the present invention.

1. A halogenated aryl ether oligomer formed by halogenation of an arylether oligomer.
 2. The oligomer of claim 1, wherein the halogen contentof the halogenated aryl ether oligomer is in the range of about 50 toabout 83 wt % of the oligomer.
 3. The oligomer of claim 1 and having anaverage of least 3 aryl rings.
 4. The oligomer of claim 1, wherein thehalogen is bromine.
 5. The oligomer of claim 1, wherein the aryl etheroligomer is brominated, comprises at least 5 aryl rings and has amolecular weight up to 1,000,000 Daltons.
 6. The oligomer of claim 1,wherein the oligomer comprises the following repeating monomeric units:

wherein R is hydrogen or alkyl, especially C₁ to C₄ alkyl, Hal ishalogen, m is at least 1, n is 0 to 3 and x is at least
 2. 7. Theoligomer of claim 6, wherein x is 5 to
 20. 8. The oligomer of claim 6,wherein Hal comprises bromine.
 9. The oligomer of claim 6, wherein saidhalogenated aryl ether oligomer also comprises end groups eachindependently comprising alkyl, alkoxy, aryl, aryloxy, hydrogen, halogenand hydroxyl.
 10. A flame retardant polymer composition comprising (a) aflammable macromolecular material and (b) a halogenated aryl etheroligomer flame retardant formed by halogenation of an aryl etheroligomer.
 11. The composition of claim 10, wherein the halogen contentof the halogenated aryl ether oligomer is in the range of about 50 toabout 83 wt % of the oligomer.
 12. The composition of claim 10 andhaving an average of least 3 aryl rings.
 13. The composition of claim10, wherein the halogen is bromine.
 14. The composition of claim 10,wherein the aryl ether oligomer is brominated, comprises at least 5 arylrings and has a molecular weight up to 1,000,000 Daltons.
 15. A flameretardant polymer composition comprising (a) a flammable macromolecularmaterial and (b) a halogenated aryl ether oligomer flame retardantformed by halogenation of an aryl ether oligomer, wherein saidhalogenated aryl ether oligomer comprises the following repeatingmonomeric units:

wherein R is hydrogen or alkyl, especially C₁ to C₄ alkyl, Hal ishalogen, m is at least 1, n is 0 to 3 and x is at least
 2. 16. Thecomposition of claim 15, wherein x is 5 to
 20. 17. The composition ofclaim 15, wherein Hal comprises bromine.
 18. The composition of claim15, wherein said halogenated aryl ether oligomer also comprises endgroups each independently comprising alkyl, alkoxy, aryl, aryloxy,hydrogen, halogen and hydroxyl.
 19. The composition of claim 15, whereinthe flammable macromolecular material (a) is a thermoplastic polymer ora thermosetting polymer.
 20. The composition of claim 15, wherein theflammable macromolecular material (a) is polystyrene and the amount ofhalogenated aryl ether oligomer flame retardant in the composition isbetween about 5 and about 25 wt %.
 21. The composition of claim 16,wherein the flammable macromolecular material (a) is polypropylene andthe amount of halogenated aryl ether oligomer flame retardant in thecomposition is between about 20 and about 50 wt %.
 22. The compositionof claim 15, wherein the flammable macromolecular material (a) ispolyethylene and the amount of halogenated aryl ether oligomer flameretardant in the composition is between about 5 and about 35 wt %. 23.The composition of claim 15, wherein the flammable macromolecularmaterial (a) is a polyamide or polyester and the amount of halogenatedaryl ether oligomer flame retardant in the composition is between about5 and about 25 wt %.
 24. A flame retardant polymer compositioncomprising (a) a flammable macromolecular material and (b) a halogenatedaryl ether having the following formula:

wherein each R¹ is independently selected from hydrogen, hydroxy,halogen and alkyl, wherein each R² is independently selected fromhydrogen, hydroxy, halogen and alkyl, provided at least one R² ishalogen, n is 5, m is 4, and x is from 1 to
 10. 25. The composition ofclaim 24, wherein x is from 2 to 6.